Vat dyestuffs containing sulfur and process of making same



. 2,768,998 VATDYESTUFFS CONTAINING SULFUR AND I PROCESS OF MAKING SAMEEmil Schwamberger, Frankfurt am Main Fechenheim, Germany, assignor .toCassela Farbwerke Mainkur Aktiengesellschaft, Frankfurt am MainFechenheim, Germany, a company of Germany No Drawing. ApplicationOctober 22, 1 952,

Serial No, 316,303

Claimspriority, application Germany- October 31, 1951 2 Claims. (Cl.260-431) The present application is a continuation-in-part of my or oneof its substitution products with a condensing agent customary for theFriedel-Crafts reaction, e. g. aluminium chloride, and a sulfurizingagent. As sulfurizing agent may be used a halide of sulfur or ofsulfurous acid, or sulfur itself. The dyestuffs thus obtained which arecharacterized by a red to red-violet color of solution in sulfuric acid,dye from a violet vat cotton and related fibres brown, yellowish oliveto yellowish green shades, most of which have excellent fastnessproperties.

It 'has now been found that compounds of the same class of dyestuffs areobtained by replacing the employed condensing agents which are customaryfor the Friedel- Crafts reaction wholly or partially by other acidiccondensing agents, in particular sulfuric acid or chlorosulfonic acid.As sulfurizing agents may be cited: sulfur or compounds capable ofdelivering sulfur, such as alkali sulfides or thiosulfates, the bluesolution of sulfur in oleum, furthermore halides of sulfur or ofsulfurous acid. The reaction may be carried out :at room temperature,with the use of cooling or at elevated temperature.

The following examples, in which the parts are parts by weight, aregiven for the purpose of illustrating the invention:

Example 1 Into 180 parts of 98% sulfuric acid, there are introduced at 70-80 C. parts of sulfur chloride and 5 parts of the dichlorodianthroneethylene obtained from 2-chloroanthrone according to German patentspecification 470,501 and stirred for about 1 /2 hours at 7080 C. Afterpouring the red-violet solution onto ice, a dyestutf containing sulfuris obtained, which dyes cotton and related fibres from a violet vatolive shades.

States PatentQ Example 2 A mixture of 80 parts of chlorosulfonic acid, 5parts of I aluminium chloride, 1.5 parts of sulfur chloride, 8 parts ofthionyl chloride and 5 parts of the starting material vat fast olivegreen shades.

Example 3 In 180 parts of sulfuric acid monohydrate, 10 parts of thedichlorodianthrone ethylene mentioned in Example 1 are dissolved. 5parts of sulfur chloride are then introduced at room temperature. Thetemperature rises somewhat and is kept at 30 C. for about 2 hours.

' After'pouring' on ice a dyestuff containing sulfur is obtained-whichdyes cotton from a violet vat fast olive green shades.

Example 4 In 180 parts of chlorosulfonic acid there are dissolved 5parts of the d-ianthrone ethylene obtainable from anthrone according toGerman patent specification 470,501. 3 parts of-sulfur chloride are thenadded followed by stirring at +5 to 10 C. for about 4 hours. Afterpouring on ice an olive green vat dyestuff is obtained. The productcontains sulfur. The color of solution in concentrated sulfuric acid iswine-red.

Exampleb Into 180 parts of chloro-sulfonic acid at 60-65 C. a

mixture of 5 parts of the dichlorodianth-rone ethylene mentioned inExamples 1 and 2 parts of finely ground sulfur is introduced and stirredfor about /2 hour at 60-65 C.

After pouring on ice the olive green product is filtered by suction,washed and dried. Thereafter, it is extracted with carbon sulfidewhereby any sulfur not being a part of the molecule is dissolved andremoved.

A vat dyestuff containing sulfur is thus obtained, which dyes cotton andrelated fibres from a violet vat olive green shades.

If in the present example sulfuric acid containing about 5% sulfuricacid anhydr-ide is used instead of chlorosulfonic acid, after a reactionduring about two hours at 3040 C. there is obtained an olive greenproduct which is partially sulfurized.

Example 6 Into parts of chlorosulfonic acid, a mixture of 5 parts of thestarting material employed in Example 1, and 4 parts of anhydrous sodiumsulfide is slowly introduced at about 40-50 C. followed by raising thetemperature to 60-65 C. until a sample given on water produces an olivegreen precipitation.

After isolating the dyestutf as indicated in Example 5, cotton is dyedfrom a violet vat olive green shades.

Example 7 10 parts of the dichlorodianthrone ethylene mentioned inExample 1 are dissolved in 180 parts of sulfuric acid monohydrate, intowhich solution a solution of 2 parts of sulfur in 50 parts of oleumhaving a content of 40% S03 is dropped. Thereafter, stirring isperformed at +5 to 10 C. until a sample taken furnishes, on introducinginto water, an olive green precipitation.

After pouring the reaction mass onto ice, an olive green product isobtained which can be freed of uncombined sulfur by a treatment withdesulfurizing agents (e. g. a 5% solution of sodium sulfide).

The dyestuff contains sulfur and dyes from a red-violet vat cotton andrelated fibres olive green shades with good fastness properties.

If the above described reaction immediately after change of color of theoriginally olive green solution to r red-violet is discontinued bypouring on ice, a product is obtained which contains sulfur and dyesfrom a violet vat violet-brown shades.

Example 8 To a solution of 10 parts of the tetrachlorodinanthroneethylene obtainable according to German patent specification 470,501from 2,6-dichloranthr0ne in 180 parts of v sulfuric acid monohydrate, asolution of 2 parts of sulfur 7 in 50 parts of oleum having a content of40% S03 is To a solution of 10 parts of the starting material employedin Example 1 in 180 parts of chlorosulfonic acid, 20 parts of potassiumxanthogenate are introduced whilst cooling. After stirring for about 20hours at room temperature, the temperature is raised to -75" C. andmaintained as long as the color of the solution becomes deep Wine-red(about /2 hour). After pouring on ice, a sulfur containing product isobtained which dyes cotton and related fibres from a violet vat brownshades.

I claim:

1. Process which comprises treating a vat dyestufi of the groupconsisting of dianthrone ethylene, dichlorodianthrone ethylene andtetrachlorodianthrone ethylene with an acidic condensing agent of thegroup consisting of sulfuric acid, fuming sulfuric acid andchlorosulfonic acid, and with a sulfurizing agent of the groupconsisting of sulfur, sulfur chloride, thionyl chloride, sodium sulfideand sodium xanthogenate to obtain a sulphur-containing dyestuif.

2. Process which comprises treating dichlorodianthrone ethylene withsulfuric acid and sulfur chloride to obtain a sulphur-containingdyestuff;

References Cited in the file of this patent Organic Reactions (Adams eta1.), vol. 3. Published by Wileyv and Sons, Inc., New York, 1947 (page 2relied on). t v a

1. PROCESS WHICH COMPRISES TREATING A VAT DYESTUFF OF THE GROUPCONSISTING OF DIANTHRONE ETHYLENE, DICHLORODIANTHRONE ETHYLENE ANDTETRACHLORODIANTHRONE ETHYLENE WITH AN ACIDIC CONDENSING AGENT OF THEGROUP CONSISTING OF SULFURIC ACID, FUMING SULFURIC ACID ANDCHLOROSULFONIC ACID, AND WITH A SULFURIZING AGENT OF THE GROUPCONSISTING OF SULFUR, SULFUR CHLORIDE, THIONYL CHLORIDE, SODIUM SULFIDEAND SODIUM XANTHOGENATE TO OBTAIN A SULPHUR-CONTAINING DYESTUFF.